EP0728810A2 - Aqueous composition for the protection of tires against ozone and migrating additives - Google Patents
Aqueous composition for the protection of tires against ozone and migrating additives Download PDFInfo
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- EP0728810A2 EP0728810A2 EP96101578A EP96101578A EP0728810A2 EP 0728810 A2 EP0728810 A2 EP 0728810A2 EP 96101578 A EP96101578 A EP 96101578A EP 96101578 A EP96101578 A EP 96101578A EP 0728810 A2 EP0728810 A2 EP 0728810A2
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0025—Compositions of the sidewalls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C13/00—Tyre sidewalls; Protecting, decorating, marking, or the like, thereof
- B60C13/002—Protection against exterior elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/056—Forming hydrophilic coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Definitions
- the invention relates to the surface condition of tires and in particular their protection against the consequences of migration to the surface of the various antioxidant and antiozonant agents which they contain.
- elastomeric compositions commonly incorporate anti-zone chemical compounds as well as waxes.
- Antiozone chemical compounds slow down the formation and propagation of cracks under static and dynamic stress conditions.
- Waxes provide additional static protection by forming a protective coating on the surface.
- protective coatings are usually used. These coatings are applied to the sidewalls after the manufacture of the tires. They are mainly made on the basis of polyvinyl alcohol (“PVA”) softened by plasticizers and include "barrier” agents, for example mica particles, to slow the migration to the surface of these anti-zone chemical agents and these waxes.
- PVA polyvinyl alcohol
- Patent US5149591 describes one of these protective coatings. However, these coatings are visible, thick, have limited mechanical strength and must be removed before the tires are actually put into service. The present invention proposes to solve these problems.
- the “glass transition temperature” of a polymer (“Tg”) is called the temperature where the mechanical behavior of the polymer changes from this vitreous, rigid and brittle behavior, to this rubbery behavior. This glass transition temperature is an essential characteristic of polymers.
- Glass transition temperatures are usually determined by differential enthalpy analysis (see Introduction to Thermal Analysis: techniques and applications - Michael E. Brown - Ed. Chapman and Hall - New York 1988). This technique, better known by the initials DSC (Differential Scanning Calorimetry), consists in determining the variations in specific heat of a sample whose temperature is raised. It makes it possible to highlight transitions or reactions which are accompanied by energy release (exothermic) or energy absorption (endothermic). The glass transition is an endothermic transition.
- the subject of the invention is an aqueous composition intended to form an anti-migration and anti-zone protective coating on the external surface of a tire, this coating being such that it does not have to be removed when these tires are actually put into service.
- component II reduces the stickiness that would have a coating formed with the preceding constituent I as the main constituent only. This stickiness is detrimental to the mechanical resistance of the coating and makes it sensitive to dust and dirt because it easily clogs.
- Component II can be a hydrophilic silica with a content by weight of between 5 and 25 parts per 100 parts of dry polymer. Preferably, the silica content is between 10 and 15 parts. In addition to the action on the stickiness, silica strengthens the mechanical properties of the coating formed.
- component II is a homopolymer or a copolymer based on at least one monomer chosen from the group of acrylic, methacrylic and vinyl monomers, said component II having a glass transition temperature above 25 ° C.
- Component II can also be polyvinyl alcohol in the proportion of 10 to 50 parts by weight per 100 parts of dry polymer.
- component II is poly (N-vinyl-2-pyrrolidone) in the proportion of 10 to 40 parts by weight per 100 parts of dry polymer.
- Component II can also be a copolymer of polyvinyl alcohol and poly (N-vinyl-2-pyrrolidone).
- this component III makes it possible to improve the wetting of the composition on the rubber surface and the mechanical resistance of the coating formed after drying.
- aqueous composition according to the invention can all advantageously comprise a hydrophilic silica in the proportion of 5 to 30 parts by weight per 100 parts of dry polymer.
- This silica has a thixotropic effect which facilitates the application of the aqueous composition to the rubber surface.
- the level of silica present in the composition makes it possible to change the appearance of the coating obtained after drying from a shiny appearance (rate from 0 to 10 parts approximately) to a matt appearance (rate of the order of 20 to 30 parts) through all the possible nuances.
- the aqueous composition according to l may also include surfactants to promote wetting on the rubber surface.
- compositions have l advantage of producing transparent coatings which do not mask the various markings affixed on the sidewalls of tires during their manufacture and their tests, these coatings can thus be used for the protection of white sidewalls.
- the aqueous composition according to the invention can also comprise pigments.
- these pigments can be carbon black to avoid bleaching of the coating obtained after prolonged contact with water or in areas of significant deformation.
- this aqueous composition can also include anti-foaming agents to facilitate application with a gun.
- the components of the aqueous composition are introduced cold.
- the mixture is stirred with known means until a complete dispersion of the products of the aqueous composition is obtained, then the emulsion obtained is filtered through a 150 ⁇ m nylon fabric to remove any small lumps of poorly dispersed material.
- the application can be done by all known means, and in particular by brush, roller or by spraying with a gun.
- the coating formed after the drying of the aqueous composition it is essential to apply the composition in one or more successive thin layers. Good results are obtained with dry coatings with a total thickness of between 1 and 30 ⁇ m. Preferably, the coatings have a thickness of 3 to 15 ⁇ m.
- the application is made to the external surface of new tires to guarantee their non-coloring by the migration of anti-zone chemical agents to the surface at least during all the transport, storage and test operations until they are put into use. service.
- the coating can be sensitive to abrasions, impacts that the sidewalls of tires in service can undergo, it has the other advantage of being removed by wear in the form of a fine crumb without peeling in a manner almost undetectable at 'eye.
- the protective coating cannot be effective on all the parts of the tire in permanent contact with the ground, such as the tread, because its wear is then very rapid. It is however very advantageous to deposit it on the entire surface because it covers and protects the tread before its use and then continues its action on all the other parts which are not in contact with the ground, such as the sides and the troughs of the sculptures.
- Example B presents the simplest solution based on a butyl acrylate / styrene copolymer.
- This polymer has a glass transition temperature of -21 ° C, consequently, the coating obtained has a rubbery behavior and is much better than the previous one in all the mechanical resistance tests with high deformations in static and dynamic.
- it is only satisfactory in the handling test, insufficient in the friction test and very insufficient in appearance during the aging test due to a sticky nature which penalizes it by making it sensitive to friction and soiling.
- Composition C is a first solution to correct this sticky nature by adding silica.
- the coating obtained is very good to excellent in all tests.
- Examples E and F are based on the same butyl acrylate / styrene copolymer to which is added polyvinyl alcohol (E) or polyvinyl pyrrolidone (F). These two coatings have very similar and very good to excellent behaviors in all tests except water resistance tests, washing and aging / mechanical strength where they are acceptable. This is due to the water solubility of these two polymers.
- the choice of a copolymer d ethyl acrylate and methyl methacrylate, as the second constituent of the aqueous composition corresponds to example G.
- the coating obtained is better than the previous two in the tests for resistance to water and to washing. Mechanical resistance to aging is also improved.
- the mechanical properties and the appearance of the coating formed can be further improved by adding silica to the composition of Example G, this is Example H.
- a preferred example of an aqueous composition according to l invention is there example I.
- Its formulation is very close to example H with a lower silica content, which gives a coating with a slightly brighter appearance.
- This formulation does not contain an anti-foaming product and this does not degrade the film's deposition properties.
- the coating obtained is transparent, which al advantage of not masking the markings affixed to the sidewall of the tires during their manufacture and their tests.
- This coating is particularly suitable for protecting the white sides that it enhances thanks to its slightly shiny appearance. There n does not have to be removed when the vehicle fitted with the tires thus coated is put into service.
- the coatings obtained are excellent in all tests. It should be noted that the resistance to scrubbing in the presence of soap is slightly lower, but it may be useful to be able to easily remove the coating in certain cases.
- silica improves the appearance of the coating obtained by giving it a slightly matt appearance (examples H, I, J, K and L).
- carbon black in Examples J, K and L improves the resistance to bleaching in the presence of water and to strong deformations.
- Example J A final specific test for ozone resistance was carried out on Example J, the so-called "Volkswagen test” test.
- the purpose of this test is to assess the ozone resistance of a tire sidewall. This is a static test carried out on a tire cut two centimeters wide taken between the bead wire and the crown plies. The cut thus produced is fixed to a tube 20 millimeters in radius by a brass wire. The surface deformation is around 12%.
- the test pieces thus conditioned are exposed in an ozone oven under the following conditions: Ozone concentration 200 ⁇ 15 pphm (share per hundred million) Relative humidity 60 ⁇ 5% Temperature 25 ⁇ 2 ° C Duration 46 hours
- the test is successful when a visual observation does not reveal any crack initiation.
- a tire was aged for four months and then half protected by a coating according to the invention. Control and protected control samples were then taken and tested.
- the control samples show pronounced cracks.
- the protected test pieces have no crack initiation on the areas protected by the coating according to the invention.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Tires In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
L'invention concerne l'état de surface des pneumatiques et particulièrement leur protection contre les conséquences des migrations vers la surface des divers agents antioxydants et antiozonants qu'ils contiennent.The invention relates to the surface condition of tires and in particular their protection against the consequences of migration to the surface of the various antioxidant and antiozonant agents which they contain.
On sait que certains polymères, et en particulier les compositions caoutchoutiques vulcanisées à base de polymères diéniques comportant des doubles liaisons éthyléniques dans leur chaîne principale sont très sensibles à l'action de l'ozone.It is known that certain polymers, and in particular vulcanized rubber compositions based on diene polymers comprising ethylenic double bonds in their main chain are very sensitive to the action of ozone.
Lorsqu'un article réalisé avec une telle composition élastomère diénique est soumis à l'action d'une contrainte en présence d'ozone, l'action néfaste de l'ozone se manifeste par l'apparition de craquelures de surface orientées perpendiculairement au sens de la contrainte. Si cette contrainte subsiste ou chaque fois qu'elle se produit les craquelures se développent et peuvent causer la rupture complète de l'article.When an article produced with such a diene elastomer composition is subjected to the action of a stress in the presence of ozone, the harmful action of ozone is manifested by the appearance of surface cracks oriented perpendicular to the direction of the constraint. If this stress persists or whenever it occurs, cracks develop and can cause the complete rupture of the article.
Pour limiter cette dégradation, les compositions élastomères incorporent couramment des composés chimiques antiozone ainsi que des cires. Les composés chimiques antiozone ralentissent la formation et la propagation des fissures dans des conditions de sollicitations statiques et dynamiques. Les cires apportent un complément de protection en statique par la formation d'un revêtement protecteur en surface.To limit this degradation, elastomeric compositions commonly incorporate anti-zone chemical compounds as well as waxes. Antiozone chemical compounds slow down the formation and propagation of cracks under static and dynamic stress conditions. Waxes provide additional static protection by forming a protective coating on the surface.
Ces moyens de lutte contre la dégradation due à l'ozone ont prouvé leur efficacité. Malheureusement, les composés antiozone les plus efficaces se caractérisent aussi par une très forte aptitude à migrer à travers leur substrat polymérique et à venir tacher et colorer les surfaces adjacentes. Par exemple, on voit apparaître à la surface des flancs des pneumatiques des taches jaunâtres ou marron. Ce phénomène est appelé "coloration". La migration en surface des cires modifie aussi l'aspect extérieur des surfaces des compositions élastomères en la rendant terne et grise. On appelle ce phénomène l'"efflorescence" des cires.These means of combating the degradation due to ozone have proven their effectiveness. Unfortunately, the most effective antiozone compounds are also characterized by a very strong ability to migrate through their polymeric substrate and to stain and color the adjacent surfaces. For example, yellowish or brown spots appear on the surface of the sidewalls of tires. This phenomenon is called "coloring". Surface migration of waxes also changes the appearance outside of the surfaces of the elastomeric compositions, making it dull and gray. This phenomenon is called the "efflorescence" of waxes.
Ces migrations sont particulièrement dommageables dans le cas des pneumatiques "à flancs blancs", mais elles peuvent aussi sérieusement pénaliser l'aspect esthétique des pneumatiques "à flancs noirs" qui voient leurs surfaces extérieures passer d'un aspect brillant à terne et grisâtre.These migrations are particularly damaging in the case of "whitewall" tires, but they can also seriously penalize the aesthetic appearance of "blackwall" tires which see their outer surfaces change from a shiny to dull and greyish appearance.
Pour préserver l'aspect esthétique des flancs blancs des pneumatiques jusqu'au moment de leur mise en service, on utilise usuellement des revêtements de protection. Ces revêtements sont appliqués sur les flancs après la fabrication des pneumatiques. Ils sont principalement réalisés à base d'alcool polyvinylique ("PVA") assoupli par des plastifiants et comprennent des agents "barrières", par exemple des particules de mica, pour ralentir la migration jusqu'à la surface de ces agents chimiques antiozone et de ces cires. Le brevet US5149591 décrit l'un de ces revêtements de protection. Mais ces revêtements sont visibles, épais, ont une résistance mécanique limitée et doivent être enlevés avant la mise en service effective des pneumatiques. La présente invention se propose de résoudre ces problèmes.To preserve the aesthetic appearance of the white sidewalls of tires until they are put into service, protective coatings are usually used. These coatings are applied to the sidewalls after the manufacture of the tires. They are mainly made on the basis of polyvinyl alcohol ("PVA") softened by plasticizers and include "barrier" agents, for example mica particles, to slow the migration to the surface of these anti-zone chemical agents and these waxes. Patent US5149591 describes one of these protective coatings. However, these coatings are visible, thick, have limited mechanical strength and must be removed before the tires are actually put into service. The present invention proposes to solve these problems.
Le comportement mécanique des polymères non réticulés varie en fonction de la température, d'une zone vitreuse aux basses températures, où le comportement est vitreux, c est-à-dire rigide et cassant, à une zone d'écoulement fluide aux températures élevées. Entre ces deux zones se trouve une zone appelée "plateau caoutchoutique" où le comportement est caoutchoutique, c'est-à-dire proche de celui d'un élastomère, dès que la masse moléculaire du polymère est suffisante pour qu'il y ait des enchevêtrements (voir : "Viscoelastic Properties of Polymers", John D. Ferry, 3rd. ed, John Wiley & Sons, 1980, notamment les chapitres 10, 12 et 13).The mechanical behavior of non-crosslinked polymers varies as a function of temperature, from a vitreous zone at low temperatures, where the behavior is vitreous, that is to say rigid and brittle, to a zone of fluid flow at high temperatures. Between these two areas is an area called "rubber plateau" where the behavior is rubbery, that is to say close to that of an elastomer, as soon as the molecular weight of the polymer is sufficient for there to be entanglements (see: "Viscoelastic Properties of Polymers", John D. Ferry, 3rd. ed, John Wiley & Sons, 1980, especially chapters 10, 12 and 13).
On appelle "température de transition vitreuse" d'un polymère ("Tg") la température où le comportement mécanique du polymère évolue de ce comportement vitreux, rigide et cassant, à ce comportement caoutchoutique. Cette température de transition vitreuse est une caractéristique essentielle des polymères.The “glass transition temperature” of a polymer (“Tg”) is called the temperature where the mechanical behavior of the polymer changes from this vitreous, rigid and brittle behavior, to this rubbery behavior. This glass transition temperature is an essential characteristic of polymers.
On détermine usuellement les températures de transition vitreuse par analyse enthalpique différentielle (voir Introduction to Thermal Analysis : techniques and applications - Michael E. Brown - Ed. Chapman and Hall - New York 1988). Cette technique, plus connue sous les initiales DSC (Differential Scanning Calorimetry), consiste à déterminer les variations de chaleur spécifique d'un échantillon dont on élève la température. Elle permet de mettre en évidence des transitions ou des réactions qui s'accompagnent de libération d'énergie (exothermique) ou d'absorption d'énergie (endothermique). La transition vitreuse est une transition endothermique.Glass transition temperatures are usually determined by differential enthalpy analysis (see Introduction to Thermal Analysis: techniques and applications - Michael E. Brown - Ed. Chapman and Hall - New York 1988). This technique, better known by the initials DSC (Differential Scanning Calorimetry), consists in determining the variations in specific heat of a sample whose temperature is raised. It makes it possible to highlight transitions or reactions which are accompanied by energy release (exothermic) or energy absorption (endothermic). The glass transition is an endothermic transition.
L'invention a pour objet une composition aqueuse destinée à former un revêtement de protection antimigrations et antiozone sur la surface extérieure d'un pneumatique, ce revêtement étant tel qu'il ne doive pas être enlevé à la mise en service effective de ces pneumatiques.The subject of the invention is an aqueous composition intended to form an anti-migration and anti-zone protective coating on the external surface of a tire, this coating being such that it does not have to be removed when these tires are actually put into service.
La composition aqueuse selon l'invention, comprend une émulsion aqueuse d'au moins :
- (a) un polymère appelé constituant I, ledit constituant I étant un homopolymère ou un copolymère à base d'au moins un monomère choisi dans le groupe des esters acryliques, méthacryliques et vinyliques, et ayant une température de transition vitreuse inférieure à 0°C; et
- (b) un constituant II choisi dans le groupe constitué par une silice hydrophile et un homopolymère ou un copolymère à base d'au moins un monomère choisi dans le groupe des monomères acryliques, méthacryliques et vinyliques, ledit homopolymère ou copolymère ayant une température de transition vitreuse supérieure à 25°C.
- (a) a polymer called component I, said component I being a homopolymer or a copolymer based on at least one monomer chosen from the group of acrylic, methacrylic and vinyl esters, and having a glass transition temperature of less than 0 ° C. ; and
- (b) a constituent II chosen from the group consisting of a hydrophilic silica and a homopolymer or a copolymer based on at least one monomer chosen from the group of acrylic, methacrylic and vinyl monomers, said homopolymer or copolymer having a glass transition temperature above 25 ° C.
Le constituant I choisi peut, notamment, être un copolymère d'acrylate de butyle et de styrène avec une teneur en poids de styrène de l'ordre de 20 %. La température de transition vitreuse d'un tel polymère est de - 21°C.The constituent I chosen can, in particular, be a copolymer of butyl acrylate and styrene with a content by weight of styrene of the order of 20%. The glass transition temperature of such a polymer is - 21 ° C.
Une telle composition aqueuse permet de former un revêtement continu, souple et adhérent sur la surface du pneumatique même en l'absence de plastifiant. Ce revêtement s'oppose aux migrations jusqu'à la surface de tous les agents antiozone présents dans les mélanges caoutchoutiques du pneumatique sans qu'il soit nécessaire d'ajouter un agent barrière tel du mica et il s'oppose par sa présence aux dégradations dues à l'ozone. Le comportement caoutchoutique du revêtement obtenu lui permet de résister à toutes les déformations subies entre la fabrication et la commercialisation des pneumatiques, et même ultérieurement.Such an aqueous composition makes it possible to form a continuous, flexible and adherent coating on the surface of the tire even in the absence of plasticizer. This coating opposes migrations to the surface of all the anti-zone agents present in the rubber mixtures of the tire without the need to add a barrier agent such as mica and it opposes by its presence the degradations due with ozone. The rubber behavior of the coating obtained enables it to resist all the deformations undergone between the manufacture and marketing of tires, and even later.
La présence du constituant II permet de réduire le caractère collant qu aurait un revêtement formé avec comme seul constituant principal le constituant I précédent. Ce caractère collant est préjudiciable à la résistance mécanique du revêtement et le rend sensible aux poussières et salissures car il s'encrasse facilement.The presence of component II reduces the stickiness that would have a coating formed with the preceding constituent I as the main constituent only. This stickiness is detrimental to the mechanical resistance of the coating and makes it sensitive to dust and dirt because it easily clogs.
Le constituant II peut être une silice hydrophile avec une teneur en poids comprise entre 5 et 25 parties pour 100 parties de polymère sec. Préférentiellement, la teneur de silice est entre 10 et 15 parties. En plus de laction sur le caractère collant, la silice renforce les propriétés mécaniques du revêtement formé.Component II can be a hydrophilic silica with a content by weight of between 5 and 25 parts per 100 parts of dry polymer. Preferably, the silica content is between 10 and 15 parts. In addition to the action on the stickiness, silica strengthens the mechanical properties of the coating formed.
Selon une variante de réalisation, le constituant II est un homopolymère ou un copolymère à base d'au moins un monomère choisi dans le groupe des monomères acryliques, méthacryliques et vinyliques, ledit constituant II ayant une température de transition vitreuse supérieure à 25°C.According to an alternative embodiment, component II is a homopolymer or a copolymer based on at least one monomer chosen from the group of acrylic, methacrylic and vinyl monomers, said component II having a glass transition temperature above 25 ° C.
Un tel constituant II peut, notamment, être un copolymère ou un mélange d'homopolymères d'acrylate d'éthyle et de méthacrylate de méthyle avec une proportion en poids d'acrylate d'éthyle de l'ordre de 55 %, ou du polyacétate de vinyle. Dans ces deux cas, la proportion en poids du constituant II est comprise entre 35 et 55 parties en poids pour 100 parties de polymère sec. En dessous de 35 parties, le caractère collant du revêtement formé est souvent encore marqué et au dessus de 55 parties, le revêtement obtenu, rigidifié, suit difficilement les déformations subies par les pneumatiques.Such a constituent II can, in particular, be a copolymer or a mixture of homopolymers of ethyl acrylate and methyl methacrylate with a proportion by weight of ethyl acrylate of the order of 55%, or of polyacetate vinyl. In these two cases, the proportion by weight of component II is between 35 and 55 parts by weight per 100 parts of dry polymer. Below 35 parts, the tackiness of the coating formed is often still marked and above 55 parts, the coating obtained, stiffened, hardly follows the deformations undergone by the tires.
Le constituant II peut aussi être de l'alcool polyvinylique dans la proportion de 10 à 50 parties en poids pour 100 parties de polymère sec.Component II can also be polyvinyl alcohol in the proportion of 10 to 50 parts by weight per 100 parts of dry polymer.
Selon un autre exemple, le constituant II est de la poly(N-vinyle-2-pyrrolidone) dans la proportion de 10 à 40 parties en poids pour 100 parties de polymère sec.According to another example, component II is poly (N-vinyl-2-pyrrolidone) in the proportion of 10 to 40 parts by weight per 100 parts of dry polymer.
Dans ces deux derniers cas, lorsque la teneur en constituant II dépasse les valeurs maximales indiquées, le revêtement formé devient trop rigide ainsi que trop sensible à l'action de l'eau.In the latter two cases, when the content of constituent II exceeds the maximum values indicated, the coating formed becomes too rigid as well as too sensitive to the action of water.
Le constituant II peut aussi être un copolymère d'alcool polyvinylique et de poly(N-vinyle-2-pyrrolidone).Component II can also be a copolymer of polyvinyl alcohol and poly (N-vinyl-2-pyrrolidone).
Selon une autre variante de l'invention, la composition aqueuse peut comprendre, en plus du constituant I et d'un constituant II composé soit d'un copolymère ou d'un mélange d'homopolymères d'acrylate d'éthyle et de méthacrylate de méthyle avec une proportion en poids d'acrylate d'éthyle de l'ordre de 55%, soit de polyacétate de vinyle, un constituant III constitué d'un homopolymère ou d'un copolymère vinylique soluble dans l'eau choisi dans le groupe des alcools polyvinyliques, des poly(N-vinyle-2-pyrrolidone) et des copolymères alcool vinylique/N-vinyle-2-pyrrolidone.According to another variant of the invention, the aqueous composition can comprise, in addition to constituent I and of constituent II composed either of a copolymer or of a mixture of homopolymers of ethyl acrylate and methacrylate of methyl with a proportion by weight of ethyl acrylate of the order of 55%, or polyvinyl acetate, a constituent III consisting of a water-soluble vinyl homopolymer or copolymer chosen from the group of polyvinyl alcohols, poly (N-vinyl-2-pyrrolidone) and vinyl alcohol / N-vinyl-2-pyrrolidone copolymers.
L'ajout de ce constituant III permet d'améliorer le mouillage de la composition sur la surface caoutchoutique et la résistance mécanique du revêtement formé après séchage.The addition of this component III makes it possible to improve the wetting of the composition on the rubber surface and the mechanical resistance of the coating formed after drying.
Avantageusement, cette variante de la composition selon l'invention dau moins trois constituants I, II et III a pour 100 parties de polymère sec :
- (a) de 50 à 75 parties de constituant I;
- (b) de 15 à 28 parties de constituant II;
- (c) de 7 à 25 parties de constituant III.
- (a) from 50 to 75 parts of constituent I;
- (b) from 15 to 28 parts of constituent II;
- (c) from 7 to 25 parts of constituent III.
Les différentes variantes de composition aqueuse selon l'invention peuvent toutes avantageusement comprendre une silice hydrophile dans la proportion de 5 à 30 parties en poids pour 100 parties de polymère sec. Cette silice a un effet thixotrope qui facilite l'application de la composition aqueuse sur la surface caoutchoutique. D'autre part, le taux de silice présent dans la composition permet de faire évoluer l'aspect du revêtement obtenu après séchage d'un aspect brillant (taux de 0 à 10 parties environ) à un aspect mat (taux de l'ordre de 20 à 30 parties) en passant par toutes les nuances possibles.The different variants of aqueous composition according to the invention can all advantageously comprise a hydrophilic silica in the proportion of 5 to 30 parts by weight per 100 parts of dry polymer. This silica has a thixotropic effect which facilitates the application of the aqueous composition to the rubber surface. On the other hand, the level of silica present in the composition makes it possible to change the appearance of the coating obtained after drying from a shiny appearance (rate from 0 to 10 parts approximately) to a matt appearance (rate of the order of 20 to 30 parts) through all the possible nuances.
Avantageusement, la composition aqueuse selon linvention peut aussi inclure des agents tensioactifs pour favoriser le mouillage sur la surface caoutchoutique.Advantageously, the aqueous composition according to l The invention may also include surfactants to promote wetting on the rubber surface.
Les compositions précédentes ont lavantage de produire des revêtements transparents qui ne masquent pas les différents marquages apposés sur les flancs des pneumatiques lors de leurs fabrications et de leurs tests, ces revêtements sont ainsi utilisables pour la protection de flancs blancs.The previous compositions have l advantage of producing transparent coatings which do not mask the various markings affixed on the sidewalls of tires during their manufacture and their tests, these coatings can thus be used for the protection of white sidewalls.
Pour donner un caractère esthétique particulier à la surface caoutchoutique protégée, la composition aqueuse selon l'invention peut aussi comprendre des pigments. En particulier, ces pigments peuvent être du noir de carbone pour éviter le blanchiment du revêtement obtenu après contact prolongé avec de l'eau ou dans les zones de déformations importantes.To give a particular aesthetic character to the protected rubber surface, the aqueous composition according to the invention can also comprise pigments. In particular, these pigments can be carbon black to avoid bleaching of the coating obtained after prolonged contact with water or in areas of significant deformation.
De façon connue, cette composition aqueuse peut aussi inclure des agents antimousse pour faciliter l'application avec un pistolet.In known manner, this aqueous composition can also include anti-foaming agents to facilitate application with a gun.
Pour préparer une composition aqueuse selon l'invention, on introduit successivement dans un récipient :
- l'eau ;
- la silice, si nécessaire ;
- le noir de carbone ou tout pigment, si nécessaire ;
- l'agent tensioactif actif ;
- l'agent anti-mousse, si nécessaire ;
- l'alcool polyvinylique ou la polyvinyle pyrrolidone selon le cas et si nécessaire ;
- le constituant I ou les constituants I et II selon le cas.
- the water ;
- silica, if necessary;
- carbon black or any pigment, if necessary;
- the active surfactant;
- anti-foaming agent, if necessary;
- polyvinyl alcohol or polyvinyl pyrrolidone as the case may be and if necessary;
- constituent I or constituents I and II as the case may be.
L'introduction des constituants de la composition aqueuse se fait à froid. On agite avec des moyens connus jusqu'à obtenir une complète dispersion des produits de la composition aqueuse, puis on filtre l'émulsion obtenue à travers une toile en nylon de 150 µm pour éliminer d'éventuels petits grumeaux de matière mal dispersée.The components of the aqueous composition are introduced cold. The mixture is stirred with known means until a complete dispersion of the products of the aqueous composition is obtained, then the emulsion obtained is filtered through a 150 μm nylon fabric to remove any small lumps of poorly dispersed material.
L'invention a aussi pour objet un procédé de protection antimigrations et antiozone d'une surface de pneumatique dans lequel :
- on applique sur ladite surface caoutchoutique une couche mince d'une composition aqueuse précédente ;
- on laisse sécher ladite couche jusqu'à la formation d'un revêtement de protection.
- a thin layer of a preceding aqueous composition is applied to said rubber surface;
- said layer is allowed to dry until the formation of a protective coating.
L'application peut se faire par tous les moyens connus, et notamment au pinceau, au rouleau ou par pulvérisation avec un pistolet.The application can be done by all known means, and in particular by brush, roller or by spraying with a gun.
Pour avoir une bonne résistance mécanique du revêtement formé après le séchage de la composition aqueuse, il est essentiel d'appliquer la composition en une ou plusieurs couches minces successives. De bons résultats sont obtenus avec des revêtements secs d'une épaisseur totale comprise entre 1 et 30 µm. Préférentiellement, les revêtements ont une épaisseur de 3 à 15 µm.To have good mechanical strength of the coating formed after the drying of the aqueous composition, it is essential to apply the composition in one or more successive thin layers. Good results are obtained with dry coatings with a total thickness of between 1 and 30 μm. Preferably, the coatings have a thickness of 3 to 15 μm.
De préférence, l'application est faite sur la surface extérieure de pneumatiques neufs pour garantir leur non coloration par la migration en surface d'agents chimiques antiozone au moins pendant toutes les opérations de transport, de stockage et de test jusqu'à leur mise en service.Preferably, the application is made to the external surface of new tires to guarantee their non-coloring by the migration of anti-zone chemical agents to the surface at least during all the transport, storage and test operations until they are put into use. service.
De plus, comme la résistance mécanique du revêtement formé est élevée, ce revêtement peut résister à toutes les opérations précédentes et rester en place après la mise en service des pneumatiques et ainsi assurer pendant plusieurs milliers de kilomètres et/ou plusieurs mois par sa présence le maintien d'un aspect esthétique de qualité ainsi qu'une protection efficace contre l'ozone.In addition, as the mechanical resistance of the coating formed is high, this coating can withstand all the preceding operations and remain in place after the tires have been put into service and thus ensure for several thousand kilometers and / or several months by its presence maintaining a quality aesthetic appearance as well as effective protection against ozone.
Même si le revêtement peut être sensible aux abrasions, chocs que peuvent subir les flancs des pneumatiques en service, il présente l'autre avantage de s'éliminer par usure sous forme d'une poudrette fine sans décollement d'une façon quasiment indécelable à l'oeil.Even if the coating can be sensitive to abrasions, impacts that the sidewalls of tires in service can undergo, it has the other advantage of being removed by wear in the form of a fine crumb without peeling in a manner almost undetectable at 'eye.
Bien entendu, le revêtement de protection ne peut pas être efficace sur toutes les parties du pneumatique en contact permanent avec le sol telle la bande de roulement car son usure est alors très rapide. Il est cependant très avantageux de le déposer sur l'ensemble de la surface car il revêt et protège la bande de roulement avant son utilisation et poursuit ensuite son action sur toutes les autres parties qui ne sont pas en contact avec le sol, telles les flancs et les fonds de creux des sculptures.Of course, the protective coating cannot be effective on all the parts of the tire in permanent contact with the ground, such as the tread, because its wear is then very rapid. It is however very advantageous to deposit it on the entire surface because it covers and protects the tread before its use and then continues its action on all the other parts which are not in contact with the ground, such as the sides and the troughs of the sculptures.
L'invention est illustrée au moyen des exemples ci-après qui ne sauraient constituer une limitation de sa portée.The invention is illustrated by means of the following examples which should not constitute a limitation of its scope.
Dans les exemples, les propriétés des compositions sont évaluées comme suit :
- "coloration/efflorescence" : test de l'aptitude du revêtement à s'opposer aux migrations en surface de tous les agents antiozone ;
- "manutention" : test de la résistance mécanique du revêtement lors d'opérations de manutention et de montage sur jante des pneumatiques (ce test impose des déformations de surface des flancs supérieures à 40 % d'extension) ;
- "tenue en dynamique" : test de la résistance mécanique du revêtement sous sollicitation dynamique, 12000 kilomètres sur une rouleuse avec une flèche imposée de 35 % à 60 kilomètres par heure, ce test impose une déformation dynamique en surface des flancs de l'ordre de 15 % d'extension ;
- "frottement " : test de la résistance mécanique du revêtement lors d'opérations de frottement des pneumatiques les uns contre les autres ;
- "râpage trottoir" : frottement du flanc revêtu d'un pneumatique contre un trottoir pendant quelques mètres, test du mode d'élimination du revêtement due à un frottement mécanique, usure en poudrette ou décollement ;
- "eau" : test de la résistance du revêtement lors d'une immersion prolongée dans l'eau, c'est une simulation du stockage longue durée d'un véhicule sur un parking dans une flaque d'eau ;
- "chaleur" : test en étuve à 50°C de la résistance du revêtement pendant au moins six mois ;
- "tenue mécanique après vieillissement" : exposition aux intempéries de pneumatiques revêtus suivie d'un test de résistance mécanique du revêtement ;
- "vieillissement/aspect" : observation visuelle de l'aspect esthétique du revêtement après dépôt et en cours de vieillissement ;
- "lavage" : test de la résistance du revêtement au lavage par frottement avec une solution aqueuse additionnée de savon ;
- "dépôt" : appréciation de la facilité d'application de la composition sur une surface caoutchoutique.
- "coloration / efflorescence": test of the ability of the coating to oppose surface migrations of all the antiozone agents;
- "handling": test of the mechanical resistance of the coating during handling and mounting operations on the rim of tires (this test requires surface deformation of the sidewalls greater than 40% of extension);
- "dynamic resistance": test of the mechanical resistance of the coating under dynamic stress, 12000 kilometers on a rolling machine with an imposed deflection of 35% at 60 kilometers per hour, this test imposes a dynamic deformation on the surface of the flanks of the order of 15% extension;
- "friction": test of the mechanical resistance of the coating during operations of friction of the tires against each other;
- "sidewalk grating": rubbing of the sidewall covered with a tire against a sidewalk for a few meters, test of the method of removing the coating due to mechanical friction, wear in crumb or peeling;
- "water": test of the resistance of the coating during prolonged immersion in water, it is a simulation of the long-term storage of a vehicle in a parking lot in a puddle;
- "heat": test in an oven at 50 ° C of the resistance of the coating for at least six months;
- "mechanical strength after aging": exposure to weathering of coated tires followed by a test of the mechanical resistance of the coating;
- "aging / appearance": visual observation of the aesthetic appearance of the coating after deposition and during aging;
- "washing": test of the resistance of the coating to washing by rubbing with an aqueous solution containing soap;
- "deposition": appreciation of the ease of application of the composition on a rubber surface.
Le tableau 1 présente les formulations des revêtements testés, et le tableau 2 les résultats obtenus. Les formulations sont présentées en prenant pour base 100 parties de polymère sec.
* Référence : Encyclopedia of Chemical Technology, 3ème édition, vol. 23.
** Référence : mesures Rhône-Poulenc.
*** Référence : mesures internes.
* Reference: Encyclopedia of Chemical Technology, 3rd edition, vol. 23.
** Reference: Rhône-Poulenc measurements.
*** Reference: internal measures.
Tous les revêtements formés avec les exemples de compositions présentés sont très bons à excellents dans le test de "coloration/efflorescence".All the coatings formed with the examples of compositions presented are very good to excellent in the "coloring / efflorescence" test.
L'exemple A concerne une composition aqueuse à base d'alcool polyvinylique (PVA) additionné de plastifiant. Ce polymère a une température de transition vitreuse élevée (+ 49°C) et ne confère pas au revêtement formé un comportement caoutchoutique aux températures usuelles de manipulation et de stockage des pneumatiques. Le revêtement obtenu est excellent en résistance aux migrations et très bons pour sa facilité d'application, en revanche, il est inacceptable dans tous les tests où des déformations importantes lui sont imposées, en statique et en dynamique, à cause de sa trop grande rigidité, en dépit de la présence du plastifiant. Cette rigidité entraîne son décollement de la surface caoutchoutique qui le reçoit.Example A relates to an aqueous composition based on polyvinyl alcohol (PVA) added with plasticizer. This polymer has a high glass transition temperature (+ 49 ° C.) and does not give the coating formed a rubbery behavior at the usual temperatures for handling and storing tires. The coating obtained is excellent in resistance to migration and very good for its ease of application, on the other hand, it is unacceptable in all tests where significant deformations are imposed on it, in static and in dynamics, because of its too great rigidity. , despite the presence of the plasticizer. This rigidity causes it to detach from the rubber surface which receives it.
L'exemple B présente la solution la plus simple à base d'un copolymère d'acrylate de butyle / styrène. Ce polymère a une température de transition vitreuse de -21°C, en conséquence, le revêtement obtenu a un comportement caoutchoutique et est bien meilleur que le précédent dans tous les tests de résistance mécanique avec des déformations élevées en statique et en dynamique. Il n'est cependant que satisfaisant en test de manutention, insuffisant en test de frottement et très insuffisant en aspect lors du test de vieillissement à cause d'un caractère collant qui le pénalise en le rendant sensible aux frottements et aux salissures.Example B presents the simplest solution based on a butyl acrylate / styrene copolymer. This polymer has a glass transition temperature of -21 ° C, consequently, the coating obtained has a rubbery behavior and is much better than the previous one in all the mechanical resistance tests with high deformations in static and dynamic. However, it is only satisfactory in the handling test, insufficient in the friction test and very insufficient in appearance during the aging test due to a sticky nature which penalizes it by making it sensitive to friction and soiling.
La composition C est une première solution pour corriger ce caractère collant grâce à l'ajout de silice. Le revêtement obtenu est très bon à excellent dans tous les tests.Composition C is a first solution to correct this sticky nature by adding silica. The coating obtained is very good to excellent in all tests.
Une autre solution est présentée avec le revêtement D, au moyen de polyacétate de vinyle. Relativement au revêtement C, D est meilleur en test de manutention et de résistance à la chaleur mais n'est qu'acceptable en résistance à l'eau à cause d'un blanchiment.Another solution is presented with coating D, using polyvinyl acetate. Relative to coating C, D is better in handling and heat resistance but is only acceptable in water resistance due to bleaching.
Les exemples E et F sont à base du même copolymère d'acrylate de butyle / styrène auquel est ajouté de l'alcool polyvinylique (E) ou de la polyvinyle pyrrolidone (F). Ces deux revêtements ont des comportements très proches et très bons à excellents dans tous les tests à l'exception des tests de résistance à l'eau, à un lavage et au vieillissement/tenue mécanique où ils sont acceptables. Cela est dû à la solubilité dans l'eau de ces deux polymères.Examples E and F are based on the same butyl acrylate / styrene copolymer to which is added polyvinyl alcohol (E) or polyvinyl pyrrolidone (F). These two coatings have very similar and very good to excellent behaviors in all tests except water resistance tests, washing and aging / mechanical strength where they are acceptable. This is due to the water solubility of these two polymers.
Le choix d'un copolymère dacrylate d'éthyle et de méthacrylate de méthyle, comme second constituant de la composition aqueuse, correspond à l'exemple G. Le revêtement obtenu est meilleur que les deux précédents dans les tests de résistance à l'eau et au lavage. La résistance mécanique au vieillissement est elle aussi améliorée.The choice of a copolymer d ethyl acrylate and methyl methacrylate, as the second constituent of the aqueous composition, corresponds to example G. The coating obtained is better than the previous two in the tests for resistance to water and to washing. Mechanical resistance to aging is also improved.
On peut améliorer encore les propriétés mécaniques et l'aspect du revêtement formé en ajoutant de la silice à la composition de l'exemple G, c'est l'exemple H.The mechanical properties and the appearance of the coating formed can be further improved by adding silica to the composition of Example G, this is Example H.
Un exemple préférentiel de composition aqueuse selon linvention est lexemple I. Sa formulation est très proche de lexemple H avec un taux de silice inférieur, ce qui donne un revêtement avec un aspect un peu plus brillant. Cette formulation ne comporte pas de produit anti-mousse et cela ne dégrade pas les propriétés de dépôt du film. Le revêtement obtenu est transparent, ce qui a lavantage de ne pas masquer les marquages apposés sur le flanc des pneumatiques au cours de leur fabrication et de leurs tests. Ce revêtement est particulièrement adapté à la protection des flancs blancs quil valorise grâce à son aspect légèrement brillant. Il na pas à être enlevé lors de la mise en service du véhicule équipé des pneumatiques ainsi revêtus..A preferred example of an aqueous composition according to l invention is there example I. Its formulation is very close to example H with a lower silica content, which gives a coating with a slightly brighter appearance. This formulation does not contain an anti-foaming product and this does not degrade the film's deposition properties. The coating obtained is transparent, which al advantage of not masking the markings affixed to the sidewall of the tires during their manufacture and their tests. This coating is particularly suitable for protecting the white sides that it enhances thanks to its slightly shiny appearance. There n does not have to be removed when the vehicle fitted with the tires thus coated is put into service.
Les exemples J, K et L correspondent à trois autres variantes préférentielles selon l'invention. La composition aqueuse est alors à base d'un mélange de trois polymères :
- AcBuSt + AE/MM + PVP : exemple J ;
- AcBuSt + AE/MM + PVA : exemple K ;
- AcBuSt + PVAc + PVP : exemple L.
- AcBuSt + AE / MM + PVP: example J;
- AcBuSt + AE / MM + PVA: example K;
- AcBuSt + PVAc + PVP: example L.
Les revêtements obtenus sont excellents dans tous les tests. Il est à noter que la résistance au lavage avec frottement en présence de savon est légèrement inférieure, mais il peut être utile de pouvoir facilement enlever le revêtement dans certains cas.The coatings obtained are excellent in all tests. It should be noted that the resistance to scrubbing in the presence of soap is slightly lower, but it may be useful to be able to easily remove the coating in certain cases.
Dans tous les cas, la présence de silice améliore l'aspect du revêtement obtenu en lui donnant un aspect légèrement mat (exemples H, I, J, K et L). Enfin, la présence de noir de carbone dans les exemples J, K et L améliore la résistance au blanchiment en présence d'eau et aux fortes déformations.In all cases, the presence of silica improves the appearance of the coating obtained by giving it a slightly matt appearance (examples H, I, J, K and L). Finally, the presence of carbon black in Examples J, K and L improves the resistance to bleaching in the presence of water and to strong deformations.
Un dernier test spécifique de la résistance à l'ozone a été réalisé sur l'exemple J, le test dit "test Volkswagen". Ce test a pour but d'évaluer la résistance à l'ozone d'un flanc de pneumatique. Il s'agit d'un test statique réalisé sur une coupe de pneumatique de deux centimètres de large prélevée entre la tringle et les nappes sommet. La coupe ainsi réalisée est fixée sur un tube de 20 millimètres de rayon par un fil de laiton. La déformation de surface est de l'ordre de 12 %. Les éprouvettes ainsi conditionnées sont exposées en étuve ozone sous les conditions suivantes :
Le test est réussi lorsqu'une observation visuelle ne révèle aucune amorce de fissure.The test is successful when a visual observation does not reveal any crack initiation.
Un pneumatique a été vieilli pendant quatre mois puis protégé par moitié par un revêtement selon l'invention. Des éprouvettes témoin - sans revêtement protecteur - et protégées ont alors été prélevées et testées.A tire was aged for four months and then half protected by a coating according to the invention. Control and protected control samples were then taken and tested.
Les éprouvettes témoin présentent des craquelures prononcées. Les éprouvettes protégées n'ont aucune amorce de craquelure sur les zones protégées par le revêtement selon l'invention..The control samples show pronounced cracks. The protected test pieces have no crack initiation on the areas protected by the coating according to the invention.
Ce test, le plus sévère de tous les tests demandés par les constructeurs automobiles, montre sans ambiguïté l'efficacité du revêtement de protection selon l'invention.This test, the most severe of all the tests requested by automobile manufacturers, unambiguously shows the effectiveness of the protective coating according to the invention.
Claims (19)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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FR9502151A FR2730740A1 (en) | 1995-02-22 | 1995-02-22 | Aq. compsn. forming anti-migration and anti-ozone coating on tyre surface |
FR9502151 | 1995-02-22 | ||
FR9512913 | 1995-10-30 | ||
FR9512913A FR2740460A3 (en) | 1995-10-30 | 1995-10-30 | Aq. compsn. forming anti-migration and anti-ozone coating on tyre surface |
Publications (3)
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EP0728810A2 true EP0728810A2 (en) | 1996-08-28 |
EP0728810A3 EP0728810A3 (en) | 1998-09-23 |
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EP96101578A Expired - Lifetime EP0728810B1 (en) | 1995-02-22 | 1996-02-05 | Method for the protection of tires against ozone and migrating additives |
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EP (1) | EP0728810B1 (en) |
JP (1) | JPH08245852A (en) |
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WO2021240109A1 (en) | 2020-05-29 | 2021-12-02 | Compagnie Generale Des Etablissements Michelin | Anti-ozonant composition for a crosslinked rubber article |
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FR2818984A1 (en) * | 2000-12-29 | 2002-07-05 | Michelin Soc Tech | PNEUMATIC HAVING COLORED METALLIC SURFACE COMPOSITION |
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US20040095244A1 (en) * | 2002-05-10 | 2004-05-20 | Kevin Conwell | Tire identification label and tire label film with integrated barrier |
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US7368147B2 (en) * | 2004-09-08 | 2008-05-06 | Baf Industries | Dressing for automobile tires, trim, and bumpers |
US7418990B2 (en) * | 2005-03-17 | 2008-09-02 | Vylasek Stephan S | Tire with acrylic polymer film |
US7837778B1 (en) * | 2005-12-05 | 2010-11-23 | Ransom Roland E Randy | Method of treating tire surfaces |
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WO2015108744A1 (en) | 2014-01-16 | 2015-07-23 | Bridgestone Americas Tire Operations, Llc | Tire with laminate and method of making same |
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- 1996-02-05 DE DE69621273T patent/DE69621273T2/en not_active Expired - Lifetime
- 1996-02-19 JP JP8030379A patent/JPH08245852A/en active Pending
- 1996-02-20 US US08/603,458 patent/US5891525A/en not_active Expired - Lifetime
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001094453A1 (en) * | 2000-06-07 | 2001-12-13 | Societe De Technologie Michelin | Method for protecting a tyre against ozone |
WO2021240109A1 (en) | 2020-05-29 | 2021-12-02 | Compagnie Generale Des Etablissements Michelin | Anti-ozonant composition for a crosslinked rubber article |
FR3110911A1 (en) | 2020-05-29 | 2021-12-03 | Compagnie Generale Des Etablissements Michelin | ANTI-OZONE PROTECTION COMPOSITION FOR A CROSS-LINKED RUBBER ARTICLE |
Also Published As
Publication number | Publication date |
---|---|
DE69621273D1 (en) | 2002-06-27 |
EP0728810A3 (en) | 1998-09-23 |
JPH08245852A (en) | 1996-09-24 |
DE69621273T2 (en) | 2002-10-31 |
EP0728810B1 (en) | 2002-05-22 |
US5977239A (en) | 1999-11-02 |
US5891525A (en) | 1999-04-06 |
ES2176368T3 (en) | 2002-12-01 |
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